On the Precise and Continuous Regulation of the Superatomic
and Spectroscopic Behaviors of the Quasi-Cubic W4C4 Cluster by the Oriented External Electric Field
posted on 2021-12-23, 18:04authored byYu-Jing Duan, Yang Zhao, Shi-Bo Cheng, Qiang Wei
Designing
and realizing novel superatoms with controllable and
tunable electronic properties is vital for their potential applications
in cluster-assembly nanomaterials. Here, we investigated the effect
of the oriented external electric field (OEEF) on the geometric and
electronic structures as well as the spectroscopic properties of the
quasi-cubic W4C4 cluster by utilizing the density
functional theory (DFT) calculations. Compared with traditional models,
the OEEF was observed to hold the special capability in continuously
and precisely modulating the electronic properties of W4C4, that is, remarkably increasing its electron affinity
(EA) (1.58 eV) to 5.61 eV under the 0.040 au OEEF (larger than any
halogen atoms in the periodic table), which possesses the superhalogen
behavior. Furthermore, the downward movement of the lowest unoccupied
molecular orbital level of the cluster accompanied by the enhancement
of the OEEF intensity was demonstrated to be the origin of the EA
increment. Additionally, the photoelectron spectra (PES) of W4C4– were also simulated under
different OEEF intensities, where the PES peaks move to a higher energy
area following the enhancement of the OEEF strength, exhibiting the
blue-shift behavior. These findings observed here open a new avenue
in conveniently and precisely adjusting the electronic properties
of clusters, which will be beneficial for the rational design of superatoms
or superatom-assembled nanomaterials under the external field.